Gold nanoparticles loaded on the special three-dimensional urchin-like micro/nano hierarchical TiO2 microspheres, with CuO layer modification, are performed for the CO preferential oxidation in H-2-rich stream at room temperature under visible light irradiation or not. It is found that the suitable outer decoration of CuO in TiO2 microspheres can obviously improve the catalytic activity of Au/TiO2, and adding visible light can further promote the performance. Based on the characterizations of catalysts, it is proposed that the CuO layer distributed on the shell of TiO2 urchin-like microspheres can enhance the electron transfer among Au, TiO2 and CuO sites to drive the increase in surface electron densities of Au and support sites induced by both the localized surface plasmon resonance of Au nanoparticles and the photo-excitation of CuO under visible light irradiation, resulting in the adsorptions and activations of CO and O-2. Therefore, as a synactic result of its unique band gap relation, its unique electron property and its morphologic effect, the novel CuO modified TiO2 support not only enhances the microstrain itself on the stabilization of the size of Au nanoparticles, but more importantly also reinforces the electron interaction between support and Au sites. (C) 2015 Elsevier B.V. All rights reserved.